Quaternary ammonium iodide for combating phytopathogenic microorganisms



United States Patent 3,279,981 QUATERNARY AMMONIUM IODIDE FOR COM-BASTING PHYTOPATHOGENIC MICROORGA- NI MS Max Geiger, Riehen, MarcHaering, Zofingen, and Hans Aebi, Riehen, Switzerland, assignors to CibaLimited, Basel, Switzerland, a Swiss company No Drawing. Filed May 20,1964, Ser. No. 369,005 Claims priority, application Switzerland, May 30,1963,.

6,817/ 63 7 Claims. (Cl. 167-22) The present invention provides apreparation for combating phytopathogenic microorganisms, whichcomprises, as active substance, a reaction product of (a) a quaternaryammonium compound with (b) a compound of iodine with an iodide,preferably Me+[I ]'-wherein Me+ represents a sodium or preferably apotassium ion in the molecular ratio of approximately a:b=l:1, togetherwith a suitable carrier.

In the preparations of the inevention, one or more of the followingadditives may be present: a vehicle, a solvent, a dispersant, anadhesive, a fertilizer and a further pesticide.

The present invention provides especially a preparation for combatingphytopathogenic microorganisms, comprising as active substance acompound of one of the following general formulae:

wherein R represents an alkyl radical containing 1 to 18 carbon atoms,or the radical having the formula wherein A represents an alkyl radicalcontaining 1 to 18 carbon atmos and n and In each represents a wholenumber from 1 to 4; R and R each represents an alkyl or I115 as whereinR represents an alkyl radical containing 1 to 18 carbon atoms or anarylalkyl radical, preferably the benzyl radical;

wherein R to R each represents a lower alkyl radical, preferably themethyl radical;

(CzH40) X wherein R represents an alkyl radical containing 1 to 18carbon atoms and R represents a lower alkyl radical, and X and Xtogether represent a value not exceeding 50;

3,279,931 Patented Oct. 18, 1966 CH3N wherein A represents an alkylradical containing 1 to 18 carbon atoms, R R and R each represents alower alkyl radical, and n is a whole number not exceeding 50;

wherein n is a whole number from 6 to 10, preferably 10 An especiallyfavorable effect is obtained when using as active substance one of thefollowing compounds CH OH;

CH t

onT-oIn-on 4 H2 on,-on, -on

The compounds of the above formulae can be prepared by mixing the aboveingredents (a) and (b) in an aqueous solution in the approximatemolecular ratio of a a:b=1: 1. The isolation of the reaction productfrom the reaction mixture is, in most cases, facilitated by the lessersolubility of the former.

The new preparations are above all potent fungicides, for example, theyare especially suitable for combating leaf spot fungi on plants.

Furthermore, mention should be made of the effect of the new compoundsagainst phytopathogenic bacteria The present invention further includesa method of combating phytopathogenic microorganisms, wherein amicrobicidal amount of one of the compounds defined above is applied tothe plants, plant seed or seedlings to be protected and/or to the soilin which the plant seeds or seedlings are to be planted.

The present invention further includes the compounds of the abovecompositions as such, insofar as they are new.

Of special significance is the fact that the active substances to beused according to the invention, when applied in a concentrationnecessary to achieve parasite control, do practically no damage to theplants treated with them.

The excellent effect of the active substances of the invention againstthe said phytopathogenic microorganisms could certainly not have beenforeseen.

In view of the very distinct differentiation in the lower plant kingdomit is, as is known, impossible to make deductions from the known actionon a certain type of microorganisms, for example bacteria, that infestthe skin, concerning genetically and oecologically differentlyconstituted microorganisms, for example, phytopathogenic fungi.

More especially, it could not have been expected that the activesubstances used in the invention, notwithstanding their very strongeffect upon the aforementioned harmful microorganisms, would not harmthe higher plants treated. It is known that quaternary active substancesvery often harm higher plants causing, for example, burning of leaves,and this danger is particularly evident in the case of very potentcompounds. The expert would certainly have expected that by usingquaternary compounds such as those used according to this invention,damage, especially burning of leaves, would occur on delicate cultureplants.

Thus, the excellent effect of the compounds to be used in the inventionupon the said phytopath-ogenic microorganisms without damaging theplants treated is certainly unexpected, more especially also in view ofthe fact that combinations of nonionic surface-active compounds withiodine/iodide complexes display strong phytotoxic side effects when usedto combat phytopathogen1c microorganisms.

The preparations of the invention containing the compounds of the aboveformulae as active substances may be used in a variety of forms ofapplication, for example pastes, powders, emulsions, suspensions,solutions or sprays.

For the manufacture of liquids suitable for direct spraying there may beused, for example, petroleum fractions of a high to medium boilingrange, preferably above 100 C., for example Diesel oil or kerosene, alsocoal tar oils and oils of vegetable or animal origin, as well ashydrocarbons for example alkylated naphthalenes andtetrahydronaphthalene, if desired in admixture with xylene mixtures,cyclohexanol, ketones, also chlorinated hydrocarbons for exampletetrachloroethane, trichloroethylene or triand tet'rachlorobenzenes.

Aqueous forms of application of the active substances to be usedaccording to the invention are obtained by dissolution of thepreparation in water, or from pastes or wettable spray powders byaddition of water. Suitable emulsifiers or dispersants are, for example,nonionic products, for example ethylene oxide condensation products ofaliphatic alcohols, amines or carboxylic acids having a long-chainhydrocarbon radical of about to carbon atoms, for example thecondensation products of octadecyl alcohol with to mols of ethyleneoxide, or of soyabean fatty acid with 30 mols of ethylene oxide, or ofcommercial oleylamine with 15 mols of ethylene oxide, or ofdodecylmercaptan with 12 mols of ethylene oxide. Suitable cationicdispersants are, for example, quaternary ammonium compounds for examplecetyl pyridinium bromide or dihydroxyethyl benzyl dodecyl ammoniumchloride. There may also be used anionic emulsifiers, preferably inconjunction with nonionic emulsifiers and/ or organic solvents.

For the manufacture of dusting and scattering preparations there may beused as solid vehicle: talcum, kaolin, bentonite, calcium carbonate,calcium phosphate, or coal, cork meal, wood meal or other mate'rals ofvegetable origin.

The preparations of the invention may be used by themselves or inconjunction with conventional pesticides, more especially insecticides,acaricides, nematocides, selective herbicides or further fungicides andbactericides.

The preparations of the invention may contain the usual additions ofsubstances that improve the distribution, adhesion, stability towardsrain or the penetration;

Example 1 (a) 500 g. of iodine were mixed with 327 g. of potassiumiodide (molecular ratio 1:1). 50 g. of Water were then stirred in, andeverything passed into solution. The resulting equimoleculariodine-iodide solution, which contained the compound K+[I was thendiluted with a further 123 g. of water.

(b) 67.8 g. (0.2 mol) of dodecyl benzyl dimethyl ammonium chloride weredissolved in 250 cc. of water. While stirring the solution well, 102 g.(0.2 mol) of the iodine-iodide solution obtained as described under (a)were then rapidly run in. The reaction product solidified; it wascomminuted in a mortar and thoroughly washed with water. The crudeproduct was recrystallized from alcohol, to yield brown crystallineflakes melting at 68 to 72 C. of the formula (OHgCHBOH):

was dried in air.

Analysis.Iodine content-calculated 34.9%, found 33.0%.

(d) 89.5 g. (0.2 mol) of the compound of the formula CHa CH3 weredissolved in 270 cc. of water. While thoroughly stirring the solution,102 g. (0.2 mol) of the iodine-iodide solution prepared as describedunder (a) were rapidly run in, to form a little mobile, tough, darkpaste which was repeatedly kneaded with water and the supernatant liquiddecanted. The reaction product of the formula C33 CH3 Gna-Q00momoomom-N-onr was dried in air.

Example 2 (a) 6 g. of the reaction product obtained under1(b) and 3 g.of an emulsifier consisting of a mixture of a nonionic and an anionicsurface-active substance (registered trademark Toximul L) [were dilutedwith xylene to 30 cc. The resulting clear solution could be diluted withwater in any desired proportion to form an emulsion ready for use as aspray broth.

(b) As described under (a) above, 6 g. of the reaction product from 1(e)and 6 g. of an emulsifier consisting of a mixture of a nonionic and ananionic surface-active substance (Toximul S, registered trademark) werediluted with xylene to 30 cc.

(c) As described under (a) above, 6 g. of the reaction product from 1(d)and 6 g. of the emulsifier described under (b) above were diluted withxylene to 30 cc.

(d) A spray powder was prepared in the following manner:

10 g. of one of the active substances used in Example 1 under (b), (c)and (d) were dissolved in 60 g. of acetone each and mixed with 79 g. ofkaolin, and the acetone was then evaporated. The residue was mixed withthe following additives; 1 g. of an emulsifier consisting of acondensation product of 1 mol of para-tertiary octylphenol with 8 molsof ethylene oxide; 10 g. of a condensation product of 1 mol offormaldehyde with 1 mol of naphthalenesulphonic acid.

Example 3 Preparation of Concentration of Efiect upon Example 2 activesubstance, Phytophthora infestans,

parts per million percent (a) 736 90. (b) 680 97. (e) 630 92.

Referred to the untreated reference plant=% effect.

(B) The effect of the preparation of Example 2(b) on Alternaria solaniwas tested under the conditions indicated under (A) above: the effectobserved was 72% (referred to the untreated reference plant=0%).

(C) The effect of the preparations of Example 2(a),

(b) and (c) on Septoria apii on celery plants was tested under theconditions indicated under (a) above; the results are listed in thefollowing table:

Preparation of Concentration of Effect of Septorz'a apii Example 2active substance, in percent parts per million Referred to the untreatedreference plant=0% efiect.

On plants treated under the conditions described under (A), (B) and (C)above, no dam-age or only an insignificant amount of damage wasobserved.

What is claimed is:

1. A method for combating phytopathogenic microorganisms without causingphytotoxic side-effects which comprises applying to an area to beprotected an effective amount of a quaternary ammonium compound of theformula wherein R represents a member selected from the group consistingof alkyl containing 1 to 18 carbon atoms, and

the radical O C.H.

\ wherein R represents a member selected from the group consisting ofalkyl containing 1 to 18 carbon atoms and benzyl is used.

3. A method as claimed in claim 1, wherein an effective amount of acompound of the formula (O2H4O)XH Rl-III\ 1112 wherein R representsalkyl containing 1 to 18 carbon atoms, R represents lower alkyl and Xand X together represents a value not exceeding 50, is used.

4. A method as claimed in claim 1, wherein an effective amount of thecompound of the formula 0H, CH -o orr2orn N r-.n

Hz(GHz) CH wherein n is a whole number from 6 to 10, is used.

5. A method as claimed in claim 1, wherein an effective amount of thecompound of the formula C H3 CH3 @l is used.

is used.

7. A method as claimed in claim 1, wherein an effective amount of thecompound of the formula is used.

GII CH OH References Cited by the Examiner UNITED STATES PATENTS JULIANS. LEVITT, Primary Examiner.

JEROME D. GOLDBERG, Assistant Examiner.

1. A METHOD FOR COMBATING PHYTOPATHOGENIC MICROORGANISMS WITHOUT CAUSINGPHYTOTOXIC SIDE-EFFECTS WHICH COMPRISES APPLYING TO AN AREA TO BEPROTECTED AN EFFECT AMOUNT OF A QUATERNARY AMMONIUM COMPOUND OF THEFORMULA